ABSTRACT
The valence electronic structure of magnetic centers is one of the factors that determines the characteristics of a magnet. This may refer to orbital degeneracy, as for jeff = 1/2 Kitaev magnets, or near-degeneracy, e.g., involving the third and fourth shells in cuprate superconductors. Here we explore the inner structure of magnetic moments in group-5 lacunar spinels, fascinating materials featuring multisite magnetic units in the form of tetrahedral tetramers. Our quantum chemical analysis reveals a very colorful landscape, much richer than the single-electron, single-configuration description applied so far to all group-5 GaM4X8 chalcogenides, and clarifies the basic multiorbital correlations on M4 tetrahedral clusters: while for V strong correlations yield a wave-function that can be well described in terms of four V4+V3+V3+V3+ resonant valence structures, for Nb and Ta a picture of dressed molecular-orbital jeff = 3/2 entities is more appropriate. These internal degrees of freedom likely shape vibronic couplings, phase transitions, and the magneto-electric properties in each of these systems.
ABSTRACT
The lacunar-spinel chalcogenides exhibit magnetic centers in the form of transition-metal tetrahedra. On the basis of density-functional computations, the electronic ground state of an Mo413+ tetrahedron has been postulated as single-configuration a12 e4 t25, where a1, e, and t2 are symmetry-adapted linear combinations of single-site Mo t2g atomic orbitals. Here we unveil the many-body tetramer wave-function: we show that sizable correlations yield a weight of only 62% for the a12 e4 t25 configuration. While spin-orbit coupling within the peculiar valence orbital manifold is still effective, the expectation value of the spin-orbit operator and the g factors deviate from figures describing nominal t5 jeff = 1/2 moments. As such, our data documents the dressing of a spin-orbit jeff = 1/2 object with intra-tetramer excitations. Our results on the internal degrees of freedom of these magnetic moments provide a solid theoretical starting point in addressing the intriguing phase transitions observed at low temperatures in these materials.
ABSTRACT
Spin-orbit quartet ground states are associated with rich phenomenology, ranging from multipolar phases in f1 rare-earth borides to magnetism emerging through covalency and vibronic couplings in d1 transition-metal compounds. The latter effect has been studied since the 1960s on t2g1 octahedral ML6 units in both molecular complexes and extended solid-state lattices. Here we analyze the Jeff = 3/2 quartet ground state of larger cubane-like M4L4 entities in lacunar spinels, composed of transition-metal (M) tetrahedra caged by chalcogenide ligands (L). These represent a unique platform where spin-orbit coupling acts on molecular-like, delocalized t2 orbitals. Using quantum chemical methods, we pin down the interplay of spin-orbit couplings in such a setting and many-body physics related to other molecular-like single-electron levels, both below and above the reference t21. We provide a different interpretation of resonant inelastic X-ray scattering data on GaTa4Se8 and, by comparing magnetic susceptibility data with calculated g factors, valuable insights into the important role of vibronic couplings.
ABSTRACT
Knowledge of the structure of the electrical double layer in ionic liquids (IL) is crucial for their applications in electrochemical technologies. We report the synthesis and applicability of an imidazolium-based amphiphilic ionic liquid with a perdeuterated alkyl chain for studies of electric potential-dependent rearrangements, and changes in the microenvironment in a monolayer on a Au(111) surface. Electrochemical measurements show two states of the organization of ions on the electrode surface. In situ IR spectroscopy shows that the alkyl chains in imidazolium cations change their orientation depending on the adsorption state. The methylene-d2 stretching modes in the perdeuterated IL display a reversible, potential-dependent appearance of a new band. The presence of this mode also depends on the anion in the IL. Supported by quantum chemical calculations, this new mode is assigned to a second νas (CD2 ) band in alkyl-chain fragments embedded in a polar environment of the anions/solvent present in the vicinity of the imidazolium cation and electrode. It is a measure of the potential-dependent segregation between polar and nonpolar environments in the layers of an IL closest to the electrode.
